This paper presents multiple-modes Scanning Probe Microscopy (SPM) studies on characterize resistance switching (RS), polarization rotation (PO) and surface potential changes in copper doped ZnO (ZnO:Cu) thin films. The bipolar RS behavior is confirmed by conductive Atomic Force Microscopy (c-AFM). The PO with almost 180° phase angle is confirmed by using the vertical and lateral Piezoresponse Force Microscopy (PFM). In addition, it elucidates that obvious polarization rotation behavior can be observed in the sample with increasing Cu concentration. Furthermore, correlation of the RS behavior with PO behavior has been studied by performing various mode SPM measurements on the same location. The electric field resulted from the opposite polarization orientation are corresponded to the different resistance states. It is found that the region with the polarization in downward direction has low resistance state (LRS), whereas the region with upward polarization has high resistance state (HRS). In addition, the Piezoresponse Force Spectroscopy (PFS) and Switching Spectroscopy PFM (SS-PFM) measurements further confirm that the existence of the built-in field due to the uncomplemented polarization may affect the depletion region and hence contribute to the RS behavior. In addition, Kelvin Probe Force Microscopy (KPFM) results show that, when ZnO-based thin films is subjected to negative and then followed by positive sample bias, injection charge limit current is dominated.
The enthalpies of dissolution of metastable rock salt and thermodynamically stable wurtzite polymorphs of zinc oxide in aqueous H2SO4 have been measured in direct calorimetric experiments at 303 K and 0.1 MPa and the obtained results enabled determination of the standard enthalpy of the rock salt-to-wurtzite phase transition in ZnO, ΔtrH = -11.7+/-0.3 kJ/mol.
The Zn K-edge X-ray absorption spectroscopy has been used to investigate in situ the decomposition of zinc peroxide (ZnO$_2$) to zinc oxide (ZnO). Principal component and linear combination analyses of the EXAFS spectra have been employed to identify the phase composition of the oxide upon heating to 900$^\circ$C. Only the ZnO$_2$ phase has been found up to 180$^\circ$C, whereas only the nanocrystalline ZnO phase has occurred above 250$^\circ$C. Detailed structural information on the temperature dependence of the local environment of zinc atoms has been obtained using the reverse Monte Carlo s…
RF sputtered ZnO and Al:ZnO films are attractive transparent conductive oxides for fabrication of opto-electronic devices. In this paper we present efforts to control carrier concentration and mobility of ZnO/Al:ZnO thin films by controlling deposition parameters (RF power, pressure and substrate temperature. Al:ZnO thin film with resistivity as low as $ρ$ = $3.8\times 10^{-4}$ $Ω$.cm at deposition temperature of 250°C has been achieved. Zinc oxide thin film with low resistivity of $ρ$ = $3.7\times 10^{-2}$ $Ω$.cm and high electron mobility of $30$ $\mathrm{cm^{-2}V^{-1}s^{-1}}$ at deposition …
Density functional theory (DFT) calculations are carried out to study the structure and electronic structure of amorphous zinc oxide (a-ZnO). The models were prepared by the "melt-quench" method. The models are chemically ordered with some coordination defects. The effect of trivalent dopants in the structure and electronic properties of a-ZnO is investigated. Models of a-X_0.375 Z_0.625 O (X=Al, Ga and In) were also prepared by the "melt- quench" method. The trivalent dopants reduce the four-fold Zn and O, thereby introducing some coordination defects in the network. The dopants prefer to bon…
Recently the successful formation of PEO coatings on zinc in a phosphate aluminate electrolyte was shown. The produced composite coatings contain various mixtures of ZnO and ZnAl$_2$O$_4$. In frame of the current study, the properties of the formed coatings including adhesion/cohesion, wear, corrosion and photocatalytic activity were analysed to identify possible applications. However, the coatings show internal porosity and a sponge-like structure. Thus the cohesion within the coating is quite low. Pull-off tests have demonstrated clear rupture within the PEO layer at strength values as low a…
The elasticity and piezoelectricity of zinc oxide (ZnO) crystals and single layers are investigated from the first-principles calculations. It is found that a ZnO thin film less than three Zn-O layers prefers a planar graphite-like structure to the wurtzite structure. ZnO single layers are much more flexible than graphite single layers in the elasticity and stronger than boron nitride single layers in the piezoelectricity. Single-walled ZnO nanotubes (SWZONTs) can exist in principle because of their negative binding energy. The piezoelectricity of SWZONTs depends on their chirality. For most Z…
Understanding the structure of ZnO surface reconstructions and their resultant properties is crucial to the rational design of ZnO-containing devices ranging from optoelectronics to catalysts. Here, we are motivated by recent experimental work which showed a new surface reconstruction containing Zn vacancies ordered in a Zn(3x3) pattern in the subsurface of (0001)-O terminated ZnO. A reconstruction with Zn vacancies on (0001)-O is surprising and counterintuitive because Zn vacancies enhance the surface dipole rather than reduce it. In this work, we show using Density Functional Theory (DFT) th…
We report persistently increased conduction in ZnO nanowires irradiated by ion beam with various ion energies and species. This effect is shown to be related to the already known persistent photo conduction in ZnO and dubbed persistent ion beam induced conduction. Both effects show similar excitation efficiency, decay rates, and chemical sensitivity. Persistent ion beam induced conduction will potentially allow countable (i.e., single dopant) implantation in ZnO nanostructures and other materials showing persistent photo conduction.
Vertically aligned, beaded zinc germinate (Zn2GeO4)/ zinc oxide (ZnO) hybrid nanowire arrays were successfully synthesized by a vapor-solid process via a catalyst-free approach. The as-synthesized products were characterized using X-ray diffraction, scanning electron microscopy and transmission electron microscopy equipped with an energy-dispersive X-ray spectrometer. TEM studies revealed the beaded microstructures of the Zn2GeO4/ZnO nanowire. Furthermore, Zn2GeO4 nanotubes were synthesized after wet etching treatments on Zn2GeO4/ZnO hybrid nanowires.
Based on first-principles calculation, it has been predicted that the magnetic anisotropy energy (MAE) in Co-doped ZnO (Co:ZnO) depends on electron-filling. Results show that the charge neutral Co:ZnO presents a "easy plane" magnetic state. While modifying the total number of electrons, the easy axis rotates from in-plane to out-of-plane. The alternation of the MAE is considered to be the change of the ground state of Co ion, resulting from the relocating of electrons on Co d-orbitals with electron-filling.
Cubic zinc oxide (rs-ZnO), metastable under normal conditions, was synthesized from the wurtzite modification (w-ZnO) at 7.7 GPa and ~800 K in the form of nanoparticles isolated in the NaCl matrix. The phase transition rs-ZnO \rightarrow w-ZnO in nanocrystalline zinc oxide under ambient pressure was experimentally studied for the first time by differential scanning calorimetry and high-temperature X-ray diffraction. It was shown that the transition occurs in the 370-430 K temperature range and its enthalpy at 400 K is -10.2 \pm 0.5 kJ mol-1.
We present a first-principles study of the atomic, electronic, and magnetic properties of two-dimensional (2D), single and bilayer ZnO in honeycomb structure and its armchair and zigzag nanoribbons. In order to reveal the dimensionality effects, our study includes also bulk ZnO in wurtzite, zincblende, and hexagonal structures. The stability of 2D ZnO, its nanoribbons and flakes are analyzed by phonon frequency, as well as by finite temperature ab initio molecular-dynamics calculations. 2D ZnO in honeycomb structure and its armchair nanoribbons are nonmagnetic semiconductors but acquire net ma…
Various defects in ZnO, focused on substitutional N$_O$ and N$_2$ in various sites, O-site, interstitial and Zn-site are studied using first-principles calculations with the goal of understanding the electron paramagnetic resonance (EPR) center reported for N$_2$ in ZnO and substitutional N on the O-site. The $g$ tensors are calculated using the gauge including projector augmented wave (GIPAW) method and compared with experiments. The $g$-tensor of the free N$_2^+$ and N$_2^-$ radicals and their various contributions within the GIPAW theory are analyzed first to provide a baseline reference fo…
The structure and electronic properties of single Cu atoms, copper monolayers and thin copper films on the polar oxygen and zinc terminated surfaces of ZnO are studied using periodic density-functional calculations. We find that the binding energy of Cu atoms sensitively depends on how charge neutrality of the polar surfaces is achieved. Bonding is very strong if the surfaces are stabilized by an electronic mechanism which leads to partially filled surface bands. As soon as the surface bands are filled (either by partial Cu coverage, by coadsorbates, or by the formation of defects), the bindin…
A density functional theory study of substitutional carbon impurities in ZnO has been performed, using both the generalized gradient approximation (GGA) and a hybrid functional (HSE06) as exchange-correlation functional. It is found that the non-spinpolarized C$_\mathrm{Zn}$ impurity is under almost all conditions thermodynamically more stable than the C$_\mathrm{O}$ impurity which has a magnetic moment of $2μ_{\mathrm{B}}$, with the exception of very O-poor and C-rich conditions. This explains the experimental difficulties in sample preparation in order to realize $d^{0}$-ferromagnetism in C-…
Hybrid field effect transistors based on the organic polymer poly(3-hexylthiophene) (P3HT) and inorganic zinc oxide were investigated. In this report we present one of the first studies on hybrid transistors employing one polymeric transport layer. The sol-gel processed ZnO was modified via Al doping between 0.8 and 10 at.%, which allows a systematic variation of the zinc oxide properties, i.e. electron mobility and morphology. With increasing doping level we observe on the one hand a decrease of the electron mobilities by two orders of magnitude,on the other hand doping enforces a morphologic…
An original modification of the standard Pulse Laser Deposition (PLD) method for preparing both undoped and indium doped zinc oxide (ZnO:In) thin films at low substrate temperature is proposed. This preparation method does not demand any further post-deposition annealing treatment of the grown films. The developed method allows to grow thin films at low substrate temperature that prevents them from the considerable loss of their intrinsic electrical and optical properties. The influence of deposition parameters on the electrical and optical parameters of the undoped and the indium doped ZnO th…
The paper presents results for zinc oxide films grown at low temperature regime by Atomic Layer Deposition (ALD). We discuss electrical properties of such films and show that low temperature deposition results in oxygen-rich ZnO layers in which free carrier concentration is very low. For optimized ALD process it can reach the level of 10^15 cm-3, while mobility of electrons is between 20 and 50 cm2/Vs. Electrical parameters of ZnO films deposited by ALD at low temperature regime are appropriate for constructing of the ZnO-based p-n and Schottky junctions. We demonstrate that such junctions are…
Zinc oxide which is a n-type semiconducting metal oxide (SMO) has been a promising material for detecting ethanol vapor. However, pure ZnO based ethanol sensors often suffer from high working temperature, cross sensitivity towards methanol and poor stability against humidity. Doping ZnO with various metal ions has been widely explored as a proficient approach to improve its ethanol sensing properties, while anionic dopants have been rarely considered. Here in we demonstrate the effect of nitrogen doping on the ethanol sensing characteristics of ZnO thin films. Nitrogen doped ZnO (N-ZnO) thin f…
During a bioInspired crystallization process, incorporation of amino acids into the crystal structure of ZnO induces lattice strain that leads to linear bandgap shifts.
The occurrence of metallic film deposition without external power supply on the copper current collector of a zinc air battery half-cell containing zinc slurry is investigated. Therefore, test specimens of miscellaneous materials representing the current collector are immersed in a commercial available zinc slurry as well as an in self-prepared zinc slurry. In case of copper and metals which are more noble (silver and gold), a coating on the respective specimen is obtained. An element mapping of the coated copper specimen is performed by means of scanning electron microscopy (SEM) and energy d…
Heterostructures of Co-doped ZnO and Permalloy were investigated for their static and dynamic magnetic interaction. The highly Co-doped ZnO is paramagentic at room temperature and becomes an uncompensated antiferromagnet at low temperatures, showing a narrowly opened hysteresis and a vertical exchange bias shift even in the absence of any ferromagnetic layer. At low temperatures in combination with Permalloy an exchange bias is found causing a horizontal as well as vertical shift of the hysteresis of the heterostructure together with an increase in coercive field. Furthermore, an increase in t…
Preliminary results on the properties of transition-metal (Ti, V, Cr, Mn, Fe, Co, Ni) $δ$-doped ZnO are reported. Using \emph{ab-initio} electronic structure calculations the magnetic order is studied assuming both the cubic rock-salt and zinc-blende structures for ZnO. The ground state magnetic order is found to depend strongly on the transition-metal atom.
This paper reports the application of zinc oxide (ZnO) in the pressure sensors that can be integrated with a microelectromechanical system (MEMS). ZnO is one of the materials that has received a great deal of attention due to its unique properties of being a semiconductor with wide bandgap and piezoelectric effects. The simpler crystal growth mechanisms of ZnO have resulted in a lower cost of ZnO-based sensors. Different types of pressure sensors based on ZnO sensing elements have also been explored. A thin circular ZnO film was simulated as a piezoelectric sensor employing the finite element …
Present paper reports the effect of ZnO additives on humidity and temperature sensing properties of cuprous oxide. The cuprous oxide powder was mixed with 10% and 25% ZnO by weight and these samples were pelletized by using hydraulic pressing machine. The sensing materials were also investigated by Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD). SEM images show morphology and porosity of material. The average particles size of cuprous oxide was found to be 1.2 micron. The sheet like structures of ZnO is evident in micrographs. From XRD all peaks are well identified and crystall…
Thin InN and GaN/InN films were grown on oxygen-polar (O) (000-1) and zinc-polar (Zn) (0001) zinc oxide (ZnO) by plasma-assisted molecular beam epitaxy (PAMBE). The influence of the growth rate (GR) and the substrate polarity on the growth mode and the surface morphology of InN and GaN/InN was investigated in situ by reflection high-energy electron diffraction (RHEED) and ex situ by atomic force microscopy (AFM). During InN deposition, a transition from two dimensional to three dimensional (2D-3D) growth mode is observed in RHEED. The critical thickness for relaxation increases with decreasing…
The study of zinc oxide, within the homogeneous electron gas approximation, results in overhybridization of zinc $3d$ shell with oxygen $2p$ shell, a problem shown for most transition metal chalcogenides. This problem can be partially overcome by using LDA+$U$ (or, GGA+$U$) methodology. However, in contrast to the zinc $3d$ orbital, Hubbard type correction is typically excluded for the oxygen $2p$ orbital. In this work, we provide results of electronic structure calculations of an oxygen vacancy in ZnO supercell from ab initio perspective, with two Hubbard type corrections, $U_{\mathrm{Zn}-3d}…
The problem of detecting the ability of some metal oxides as photocatalysts is receiving considerable attention in the world. The studied zinc oxide is considered as one of the most utilized semiconductors, due to its direct band gap of 3.37 eV and a large exciton binding energy of 60 meV at room temperature. The characteristic formulation of Copper doped zinc oxide is implemented to obtain an improved adsorption kinetics and photocatalytic activity of zinc oxide photocatalyst capable of evolving estimated photoluminescence (PL) spectra of zinc oxide nanoparticles to explore the effect of Copp…
Cobalt-doped ZnO (Co2+:ZnO) films were studied by magnetic circular dichroism (MCD) spectroscopy. A broad 300 K ferromagnetic MCD signal was observed between 1.4 and 4.0 eV after introducing shallow donor states by exposure of paramagnetic Co2+:ZnO films to zinc vapor. The new sub-bandgap ferromagnetic MCD intensity is attributed to low-energy photoionization transitions originating from a spin-split donor impurity band in ferromagnetic Co2+:ZnO.
Nanostructured Zinc oxide (ZnO) was synthesized via a ball milling for 10 hours using high energy planetary ball mill. Phase purity and homogeneity of all the samples have been investigated by X-ray diffraction (XRD) and Field Emission Scanning Electron Microscopy (FE-SEM). All the diffraction peaks can be indexed to the hexagonal phase ZnO with hexagonal symmetry (space group P63mc). Average crystallite size was observed to be 20 nm. There was a remarkable suppression in thermal conductivity (κ) compared to the bulk values by a factor of ~50 at room temperature. This suggests to the possibili…
The micro-properties (structure and composition), and macro-properties (electrical and optical properties) of zinc oxide (ZnO) thin films deposited on glass substrates using a filtere vacuum arc deposition (FVAD) system were investigated as a function of oxygen pressure (0.37 - 0.5 Pa) and arc current (100 - 300 A). Correlations between the various properties were investigated.
Ion implantation is an interesting method to dope semiconducting materials such as zinc oxide provided that the implantation-induced defects can be subsequently removed. Nitrogen implantation followed by anneals under O2 were carried out on zinc oxide nanowires in the same conditions as in a previous study on bulk ZnO [J. Appl.Phys. 109, 023513 (2011)], allowing a direct comparison of the defect recovery mechanisms. Transmission electron microscopy and cathodoluminescence were carried out to assess the effects of nitrogen implantation and of subsequent anneals on the structural and optical pro…
We review pitfalls in recent efforts to make a conventional semiconductor, namely ZnO, ferromagnetic by means of doping with transition metal ions. Since the solubility of those elements is rather low, formation of secondary phases and the creation of defects upon low temperature processing can lead to unwanted magnetic effects. Among others, ion implantation is a method of doping, which is highly suited for the investigation of those effects. By focussing mainly on Fe, Co or Ni implanted ZnO single crystals we show that there are manifold sources for ferromagnetism in this material which can …
Ionic layer epitaxy (ILE) has recently been developed as an effective strategy to synthesize nanometer-thick 2D materials with a non-layered crystal structure, such as ZnO. The packing density of the amphiphilic monolayer is believed to be a key parameter that controls the nanosheet nucleation and growth. In this work, we systematically investigated the growth behavior of single-crystalline ZnO nanosheets templated at the water-air interface by an anionic oleylsulfate monolayer with different packing densities. The thicknesses of ZnO nanosheets were tuned from one unit cell to four unit cells,…
The accurate absolute surface energies of (0001)/(000-1) surfaces of wurtzite structures are crucial in determining the thin film growth mode of important energy materials. However, the surface energies still remain to be solved due to the intrinsic difficulty of calculating dangling bond energy of asymmetrically bonded surface atoms. In this study, we used a pseudo-hydrogen passivation method to estimate the dangling bond energy and calculate the polar surfaces of ZnO and GaN. The calculations were based on the pseudo chemical potentials obtained from a set of tetrahedral clusters or simple p…
The wide bandgap semiconductor ZnO is interesting for spintronic applications because of its small spin-orbit coupling implying a large spin coherence length. Utilizing vertical spin valve devices with ferromagnetic electrodes (TiN/Co/ZnO/Ni/Au), we study the spin-polarized transport across ZnO in all-electrical experiments. The measured magnetoresistance agrees well with the prediction of a two spin channel model with spin-dependent interface resistance. Fitting the data yields spin diffusion lengths of 10.8nm (2K), 10.7nm (10K), and 6.2nm (200K) in ZnO, corresponding to spin lifetimes of 2.6…
Magnetic properties of Re substituting for the divalent Zn ions and impurity pairs in wurtzite and zinc blende ZnO are analyzed by employing the Generalized Gradient Approximation with the +U corrections. The +U term applied to d(Zn), p(O), and d(Re) orbitals stabilizes spin polarization of Re. Re impurity introduces a defect level located in the band gap, and Re2+ generates the local spin 5/2 in both wurtzite and zinc blende structures. Magnetic coupling of Re-Re pairs as a function of distance between the defects, their relative orientation, and the charge state was calculated. All magnetic …
The spectral characteristics of ZnO:Ga and ZnO:Ga,N ceramics prepared by uniaxial hot pressing have been investigated. At room temperature, the edge (exciton) band at 3.12 eV dominates in the luminescence spectra of ZnO:Ga, while a wide luminescence band at 2.37 eV, which is likely to be due to zinc vacancies, is observed in the spectra of ZnO:Ga,N. Upon heating, the edge band maximum shifts to lower energies and the bandwidth increases. The extrapolated position of the edge-band maximum at zero temperature, Em(0) = 3.367 +/- 0.005 eV, is in agreement with the data for thin zinc oxide films. T…
Nanocomposite thin films of Zinc Oxide and Silicon were grown by co-evaporating powdered ZnO and Si. This resulted in nanocrystallites of ZnO being embedded in Silicon. The mismatch in crystal structures of constituent materials result in the ZnO nanocrystals to exist in a state of stress. This along with oxygen vacancies in the samples result in good Photoluminescence emission at 520nm. Also, Silicon background gave a photoluminescence emission at 620nm. The structure was found quite stable over time since the homgenously dispersed ZnO nanocrystals do not agglomerate. The nanocomposites promi…
The formation energies and electronic structure of europium doped zinc oxide has been determined using DFT and many-body $GW$ methods. In the absence of intrisic defects we find that the europium-$f$ states are located in the ZnO band gap with europium possessing a formal charge of 2+. On the other hand, the presence of intrinsic defects in ZnO allows intraband $f-f$ transitions otherwise forbidden in atomic europium. This result coorroborates with recently observed photoluminescence in the visible red region [1].
Objective of this work was to synthesize Copper doped Zinc Oxide (CZO) films and optimization of process parameters by varying molarity of zinc acetate dehydrate from 0.5 M to 1.0 M, concentration of copper acetate monohydrate from 1% to 5 % and annealing temperature from 200 C to 300 C to measure the sensitivity of CZO films for CO (Carbon Monoxide) gas. The concentration of CO gas was maintained at 5 ppm and operating temperature of 250 oC was used for sensing. Analysis for sensitivity showed highest grading for parametric combination of 0.75 molarity, 3% copper concentration and 300 C annea…
Identification of complex defect has been a long-sought-after physics problem for controlling the defect population and engineering the useful properties in wide bandgap oxide semiconductors. Here we report a systematic study of (GaZn-VZn)- acceptor complex defect via zinc self-diffusion in Ga-doped ZnO isotopic heterostructures, which were conceived and prepared with delicately controlled growth conditions. The secondary ion mass spectrometry and temperature-dependent Hall-effect measurements reveal that a high density of controllable (GaZn-VZn)- is the predominant compensating defect in Ga-d…
Zinc oxide (ZnO) is the most important material for the fabrication of modern varistors (variable resistors). It is known that the highly nonlinear current-voltage relationship of ZnO varistors is due to effects taking place at the grain boundaries. For an accurate investigation of the mechanism of this process, techniques are required that allow a direct observation of local electric fields in varistor samples. The objective of this study is to show that an atomic force microscope in a set-up as an electrostatic force microscope is capable of the in-situ observation and measurement of an appl…
Nanocomposite films of Zinc Oxide and Silicon were grown by thermal evaporation technique using varying ratios of ZnO:Si in the starting material. Analysis reveal the role of ZnO and amorphous silicon interface in contributing to relatively less common blue photoluminescence emissions (at $\sim$ 400 and 470nm). These blue peaks are observed along with the emissions resulting from band edge transition (370nm) and those related to defects (522nm) of ZnO. Careful analysis shows that along with the grain size of ZnO, a suitable compositional ratio (of ZnO to silicon) is critical for the coexistenc…
Ceramics ZnO:Zn of 20mm diameter and 1.6mm thickness with an optical transparency up to 0.33 in the visible region have been prepared by hot pressing technique. Scintillating and luminescent characteristics such as emission spectra, decay time, yield, and TSL glow curve have been measured under X-ray excitation. Two emission bands peaking at 500 and 380 nm were detected, the light output was about 80% of that for standard BGO scintillator, main decay constant was 10.4 +/- 0.1 ns. The obtained data allow us to consider the ZnO:Zn ceramics as a perspective scintillator. Finally, the investigatio…
Crystalline wurtzite zinc oxide (w-ZnO) can be used as a wide band gap semiconductor for light emitting devices and for transparent or high temperature electronics. The use of amorphous zinc oxide (a-ZnO) can be an advantage in these applications. In this paper we report on X-ray amorphous a-ZnOx thin films (~500 nm) deposited at cryogenic temperatures by reactive magnetron sputtering. The substrates were cooled by a nitrogen flow through the copper substrate holder during the deposition. The films were characterized by X-ray diffraction (XRD), Raman, infrared, UV-Vis-NIR spectroscopies, and e…
The data of experimental studies of optical characteristics of colloidal solutions, composition and morphology of its dispersed phase, resulting from laser ablation of zinc in aqueous solutions of anionic surfactants --- sodium dodecyl sulfate (SDS), dioctyl sodium sulfosuccinate (AOT) are presented. It is shown that by studying the optical absorption spectra of the colloid, X-ray spectra and AFM-images of extracted from colloid solid phase, it is possible to trace the dynamics of ZnO nanostructures formation from zinc nanoclasters size of several nanometers to ZnO fractal aggregates (FA) size…
Ferrite nanocrystals are interesting material due to their rich physical properties. Here we add nonmagnetic dopants Zn and Cu to nickel ferrite nanocrystals, Ni1-xMxFe2O4 (0<=x<=1, M{\in}{Cu, Zn}), and characterize how relevant properties of the samples are modified accordingly. Basically, these dopings cause a rearrangement of Fe+3 ions into the two preexisting octahedral and tetrahedral sites. In fact, this, we show, induces pertinent magnetic properties of the doped samples. In the case of the Cu-doping, the Jahn-Teller effect also emerges, which we identify through the FTIR Spectroscopy o…
Recently the point defect responsible for the intra-3$d$ luminescence of cobalt in doped ZnO samples has been indentified\,\cite{pssb2019}. In this work we further extend our investigation to other point defects in Co-doped ZnO. We use density-functional theory and GW calculations to determined the orbital-resolved band structure of cobalt doped zinc oxide (ZnO). We show that mainly O-p and Co-d orbitals take part in the process and confirm that an oxygen interstitial nearby a cobalt atom is a likely defect to occur in Co-implanted ZnO samples. We also rule out that other common point defects …
During the past years there has been renewed interest in the wide-bandgap II-VI semiconductor ZnO, triggered by promising prospects for spintronic applications. First, ferromagnetism was predicted for dilute magnetic doping. In comprehensive investigation of ZnO:Co thin films based on the combined measurement of macroscopic and microscopic properties, we find no evidence for carrier-mediated itinerant ferromagnetism. Phase-pure, crystallographically excellent ZnO:Co is uniformly paramagnetic. Superparamagnetism arises when phase separation or defect formation occurs, due to nanometer-sized met…
The exploration of new catalysts for the vapor-liquid-solid (VLS) synthesis of one-dimensional (1-D) materials promises to yield new morphologies and functionality. Here, we show, for the model ZnO system, that this possible using a semiconductor (Ge) catalyst. In particular, two unusual morphologies are described: twisted nanowires and twisted nanotubes, in addition to the usual straight nanowires. The twisted nanotubes show large hollow cores and surprisingly high twisting rates (up to 9o/μm), which cannot be easily explained through the Eshelby twist model. A combination of ex situ and in s…
We demonstrate heavy and hyper doping of ZnO by a combination of gallium (Ga) ion implantation using a focused ion beam (FIB) system and post-implantation laser annealing. Ion implantation allows for the incorporation of impurities with nearly arbitrary concentrations, and the laser-annealing process enables dopant activation close to or beyond the solid-solubility limit of Ga in ZnO. We achieved heavily doped ZnO:Ga with free-carrier concentrations of ~10^21 cm^(-3), resulting in a plasma wavelength of 1.02 um, which is substantially shorter than the telecommunication wavelength of 1.55 um. T…
We use real-time spectroscopic polarimetric observations of growth and a chemical model derived therefrom, to develop a method of growing dense, two-dimensional zinc oxide epitaxially on sapphire by metalorganic chemical vapor deposition. Particulate zinc oxide formed in the gas phase is used to advantage as the deposition source. Our real-time data provide unequivocal evidence that: a seed layer is required; unwanted fractions of ZnO are deposited; but these fractions can be removed by cycling between brief periods of net deposition and etching. The transition between deposition and etching o…
The effect of applying an external electric field on doping-induced spin-orbit splitting of the lowest conduction-band states in a bismuth-doped zinc oxide nanowire is studied by performing electronic structure calculations within the framework of density functional theory. It is demonstrated that spin splitting in Bi-doped ZnO nanowires could be tuned and enhanced electrically via control of the strength and direction of the applied electric field, thanks to the nonuniform and anisotropic response of the ZnO:Bi nanowire to external electric fields. The results reported here indicate that a si…
We propose a first-principle method for evaluations of the time-dependent electron distribution function of excited electrons in the conduction band of semiconductors. The method takes into account the excitations of electrons by external source and the relaxation to the bottom of conduction band via electron-phonon coupling. The methods permits calculations of the non-equilibrium electron distribution function, the quasi-stationary distribution function with steady-in-time source of light, the time of setting of the quasi-stationary distribution and the time of energy loss via relaxation to t…
A novel sol-gel route to c-axis orientated undoped and Co, Fe, Mn and V doped ZnO films is reported. Sols were prepared from a hydrated zinc acetate precursor and dimethyl formamide (DMF) solvent. Films were spin-coated on to hydrophilic sapphire substrates then dried, annealed and post-annealed, producing almost purely uniaxial ZnO crystallites and a high degree of long-range structural order. Specific orientation of hexagonal crystallites is demonstrated both perpendicular and parallel to the substrate surface. Cobalt doping resulted in the formation of columnar ZnO nanocrystals. Vanadium do…
Positively charged zinc oxide clusters ZnnOm (up to n = 16, m <= n) of various stoichiometry were synthesized in the gas phase by excimer ArF laser ablation of a ZnO target and investigated using time-of-flight mass spectrometry. Depending on ablation conditions, either metal rich or stoichiometric clusters dominate in the mass spectrum. When the irradiated target surface is fairly fresh, the most abundant clusters are metal rich with Zn(n+1)On and Zn(n+3)On being the major series. The stoichiometric clusters are observed with an etched ablated surface. The magic numbers at n = 9, 11 and 15 in…
